Quaternary ammonium amide and/or ester salts

ABSTRACT

The invention relates to quaternary ammonium amide and/or ester salts and their use as additives, including their use in fuels, such as diesel fuel. The invention particularly relates to the use of quaternary ammonium amide and/or ester salts as detergents in diesel fuels.

FIELD OF THE INVENTION

The invention relates to quaternary ammonium amide and ester salts,processes for making them, and their use as additives, including theiruse in fuels, such as diesel fuel and fuel oils. The inventionparticularly relates to the use of quaternary ammonium amide and estersalts as detergents in fuels and the methods of making them.

BACKGROUND OF THE INVENTION

Hydrocarbon fuels generally contain numerous deposit-forming substances.When used in internal combustion engines (ICEs), deposits tend to formon and around constricted areas of the engine which are in contact withthe fuel. In automobile engines deposits can build up on engine intakevalves leading to progressive restriction of the gaseous fuel mixtureflow into the combustion chamber and to valve sticking. There are twogeneral types of inlet valve deposits, heavy deposits and thin deposits.These different types of deposits affect the performance of the fuel andthe engine in slightly different ways. Heavy deposits are carbonaceousand oily in appearance. They cause flow restriction past the valves,which in turn reduces the maximum power of the engine, decreasing fueleconomy and increasing emissions. Thin deposits tend to cause problemson starting the engine and increasing emissions.

As engines become more sensitive to deposits, it has become commonpractice to incorporate a detergent in the fuel composition for thepurposes of inhibiting the formation, and facilitating the removal, ofengine deposits, thereby improving engine performance and emissions.

It is known to use certain polyisobutylsuccinimide-derived quaternizedPIB/amine dispersants/detergents as additives in fuel compositions.Polyisobutylsuccinimides may also be described as polyisobutylenesuccinimides. These quaternized dispersants/detergents are derived fromtraditional PIB/amine fuel additive compounds that have pendant tertiaryamine sites which can be alkylated, i.e. quaternized, by a quaternizingagent, such as propylene oxide. Examples of these additives aredisclosed in U.S. patent application US 2008/0307698.

However, there is a need for additives that provide the benefitsdescribed above while also exhibiting improved thermal stability and/oroil compatibility properties. There is also a need for additives thatprovide the benefits described above more efficiently, thus allowing forthe use of lower additive treat rates while obtaining the sameperformance, thus reducing the cost and environmental impact of theadditives as well as the compositions in which they are used. There isalso a need for additives that provide the benefits described abovewhich are less energy intensive to produce.

The present invention deals with a new class of detergents which offersignificant improvements over traditional PIB/amine detergents,including polyisobutylsuccinimide-derived quaternized detergents. A newclass of quaternized PIB/amines derived from polyisobutenyl succinamidesand/or esters have now been discovered. These additives are morethermally stable than the imide variant and may be manufactured by aless energy-intensive process. The quaternized additives of the presentinvention not only perform at least equally as well as comparablepolyisobutenyl succinimide quaternized additives, but can also providethat performance more efficiently and/or with improved thermal stabilityand/or oil compatibility.

SUMMARY OF THE INVENTION

The present invention provides a composition containing a quaternaryammonium amide and/or quaternary ammonium ester salt detergent, wherethe quaternized detergent comprises the reaction product of: (a) anon-quaternized amide and/or ester detergent having a tertiary aminefunctionality; and (b) a quaternizing agent. These additives may bederived from non-quaternized polyisobutylsuccinamides and/or esters,which are dispersants/detergents that have tertiary amine functionalityand an amide and/or ester group, as opposed to the imide groupcontaining materials discussed above.

The invention further provides for these additives and the methods ofmaking them, where the additives are formed by a reaction completed inthe presence of a protic solvent and/or is essentially free to free ofany additional acid component other than the acid group(s) present inthe structure of the detergent itself. The invention includesembodiments where the non-quaternized detergent is the condensationproduct of a hydrocarbyl-substituted acylating agent and a compoundhaving an oxygen or nitrogen atom capable of condensing with the agent.

The present invention also provides fuel and additive concentratecompositions containing the additive described herein, where suchcompositions may further contain a fuel, and optionally one or moreadditional fuel additives.

The invention also provides for a process of making the additivesdescribed herein where the process includes: reacting a non-quaternizedamide and/or ester detergent having a tertiary amine functionality witha quaternizing agent; thereby obtaining the quaternized detergent.

The processes of the present invention can include the steps of: (1)mixing a non-quaternized amide and/or ester detergent having an aminefunctionality, a quaternizing agent and a protic solvent; (2) heatingthe mixture to a temperature between about 50° C. to about 130° C.; (3)holding for the reaction to complete; thereby obtaining the quaternizedamide and/or ester detergent. In some embodiments the process is free ofthe addition of any acid reactant, such as acetic acid. The product isobtained despite the absence of such an acid reactant.

The present invention further provides methods of operating internalcombustion engines and/or open flame burners comprising supplying to theengines and/or open flame burners the fuel compositions describedherein. The present invention also provides for the use of theseadditives as fuel detergents.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

The Quaternary Ammonium Amide and/or Ester Salt Detergent

The quaternary amide and/or ester detergents of the present inventionmay be described as the reaction product of: (a) a non-quaternized amideand/or ester detergent having a tertiary amine functionality; and (b) aquaternizing agent. In some embodiments the non-quaternized detergent isthe condensation product of (i) a hydrocarbyl-substituted acylatingagent and (ii) a compound having an oxygen or nitrogen atom capable ofcondensing with said acylating agent and further having at least onetertiary amino group.

a. The Non-Quaternized Amide and/or Ester Detergent

The non-quaternized amide and/or ester detergents suitable for use inthe present invention include the condensation product of (i) ahydrocarbyl-substituted acylating agent and (ii) a compound having anoxygen or nitrogen atom capable of condensing with said acylating agentand further having at least one tertiary amino group, where theresulting detergent has at least one tertiary amino group and alsocontains an amide group and/or an ester group. Typically, the compoundhaving an oxygen or nitrogen atom capable of condensing with saidacylating agent determined whether the resulting detergent contains anamide group or an ester group. In some embodiments, the non-quaternizeddetergent, and so the resulting quaternized detergent is free of anyimide groups. In some embodiments, the non-quaternized detergent, and sothe resulting quaternized detergent is free of any ester groups. Inthese embodiments the detergent contains at least one, or just one,amide group.

The hydrocarbyl substituted acylating agent can be the reaction productof a long chain hydrocarbon, generally a polyolefin reacted with amonounsaturated carboxylic acid reactant, such as, (i)α,β-monounsaturated C₄ to C₁₀ dicarboxylic acid, such as, fumaric acid,itaconic acid, maleic acid; (ii) derivatives of (i) such as anhydridesor C₁ to C₅ alcohol derived mono- or di-esters of (i); (iii)α,β-monounsaturated C₃ to C₁₀ monocarboxylic acid such as acrylic acidand methacrylic acid; or (iv) derivatives of (iii), such as, C₁ to C₅alcohol derived esters of (iii) with any compound containing an olefinicbond represented by the general formula:(R¹)(R²)C═C(R⁶)(CH(R⁷)(R⁸))  (I)wherein each of R¹ and R² is independently hydrogen or a hydrocarbonbased group; each of R⁶, R⁷ and R⁸ is independently hydrogen or ahydrocarbon based group and preferably at least one is a hydrocarbylgroup containing at least 20 carbon atoms.

Olefin polymers suitable for reaction with the monounsaturatedcarboxylic acids include polymers comprising a major molar amount of C₂to C₂₀, e.g. C₂ to C₅, monoolefin. Such olefins include ethylene,propylene, butylene, isobutylene, pentene, octene-1, or styrene. Thepolymers can be homopolymers such as polyisobutylene, as well ascopolymers of two or more such olefins, such as copolymers of: ethyleneand propylene; butylene and isobutylene; or propylene and isobutylene.Other copolymers include those in which a minor molar amount of thecopolymer monomers, e.g. 1 to 10 mole percent, is a C₄ to C₁₈ diolefin,e.g. a copolymer of isobutylene and butadiene or a copolymer ofethylene, propylene and 1,4-hexadiene.

In one embodiment, at least one R group of formula (I) is derived frompolybutene, i.e. polymers of C₄ olefins including 1-butene, 2-butene andisobutylene. Suitable C₄ polymers include polyisobutylene. In anotherembodiment, at least one R group of formula (I) is derived fromethylene-alpha olefin polymers, including ethylene-propylene-dienepolymers. Ethylene-alpha olefin copolymers and ethylene-lowerolefin-diene terpolymers are described in numerous patents, includingEuropean patent publication EP 0 279 863 and the following U.S. Pat.Nos. 3,598,738; 4,026,809; 4,032,700; 4,137,185; 4,156,061; 4,320,019;4,357,250; 4,658,078; 4,668,834; 4,937,299; 5,324,800.

In another embodiment, the olefinic bonds of formula (I) arepredominantly vinylidene groups, represented by the following formulas:

wherein R is a hydrocarbyl group

wherein R is a hydrocarbyl group.

In one embodiment, the vinylidene content of formula (I) can comprise atleast about 30 mole percent having terminal vinylidene groups, at leastabout 50 mole percent having terminal vinylidene groups, or at leastabout 70 mole percent having terminal vinylidene groups. Such materialand methods for preparing them are described in U.S. Pat. Nos.5,071,919; 5,137,978; 5,137,980; 5,286,823, 5,408,018, 6,562,913,6,683,138, 7,037,999 and U.S. publications: 20040176552A1, 20050137363and 20060079652A1. Such products are commercially available by BASF,under the trade name GLISSOPAL™ and by Texas Petrochemical LP, under thetrade name TPC 1105™ and TPC 595™

Methods of making hydrocarbyl substituted acylating agents from thereaction of monounsaturated carboxylic acid reactants and compounds offormula (I) are well know in the art and disclosed in: U.S. Pat. Nos.3,361,673 and 3,401,118 to cause a thermal “ene” reaction to take place;U.S. Pat. Nos. 3,087,436; 3,172,892; 3,272,746, 3,215,707; 3,231,587;3,912,764; 4,110,349; 4,234,435; 6,077,909; and 6,165,235.

In one embodiment, the hydrocarbyl-substituted acylating agent is adicarboxylic acylating agent. In some of these embodiments, thehydrocarbyl-substituted acylating agent comprises polyisobutylenesuccinic anhydride.

In another embodiment, the hydrocarbyl substituted acylating agent canbe made from the reaction of at least one carboxylic reactantrepresented by the following formulas:

wherein each of R³, R⁵ and R⁹ is independently H or a hydrocarbyl group;R⁴ is a divalent hydrocarbylene group; and n is 0 or 1 with any compoundcontaining an olefin bond as represented by formula (I). Compounds andthe processes for making these compounds are disclosed in U.S. Pat. Nos.5,739,356; 5,777,142; 5,786,490; 5,856,524; 6,020,500; and 6,114,547.

Still other hydrocarbyl substituted acylating agents may be used, thoughsome will produce less stable quaternary salts. In one embodiment theagent is the reaction of a compound of formula (I) with a compound offormula (IV) or (V), where the reaction can optionally be carried out inthe presence of at least one aldehyde and/or ketone, such asformaldehyde, or reactive equivalents thereof. Such compounds and theprocesses for making them are disclosed in U.S. Pat. Nos. 5,840,920;6,147,036; and 6,207,839. In another embodiment, the hydrocarbylsubstituted acylating agent can include methylene bis-phenol alkanoicacid compounds, the condensation product of (i) an aromatic compound and(ii) at least one carboxylic reactant such as the compounds of formula(IV) and (V) described above. The reaction of (i) with (ii) may becarried out in the presence of at least one aldehyde and/or ketone. Thereaction may also be carried out in the presence of an acidic catalystsuch as organic sulfonic acids, heteropolyacids, and mineral acids. Suchcompounds and the processes for making them are disclosed in U.S. Pat.Nos. 3,954,808; 5,336,278; 5,458,793; 5,620,949; 5,827,805; and6,001,781. Other methods of making hydrocarbyl substituted acylatingagents can be found in U.S. Pat. Nos. 5,912,213; 5,851,966; and5,885,944.

The non-quaternized amide and/or ester detergent used to prepare theadditives of the present invention are themselves formed when theacylating agents described above are reacted with a compound having anoxygen or nitrogen atom capable of condensing with the acylating agentwhich further has at least one tertiary amino group.

In one embodiment, the compound having an oxygen or nitrogen atomcapable of condensing with the acylating agent and further having atertiary amino group is represented by the following formulas:

wherein X is a alkylene group containing 1 to 4 carbon atoms and R², R³and R⁴ are hydrocarbyl groups; and

wherein X is a alkylene group containing 1 to 4 carbon atoms and R³ andR⁴ are hydrocarbyl groups.

Examples of nitrogen or oxygen containing compounds capable ofcondensing with the acylating agents, which also have a tertiary aminogroup include but are not limited to: 1-aminopiperidine,1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-pipecoline,1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolidinyl)piperidine,1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine,N,N-diethylethylenediamine, N,N-dimethylethylenediamine,N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane,N,N-dimethyl-1,3-diaminopropane, N,N,N′-trimethylethylenediamine,N,N-dimethyl-N′-ethylethylenediamine,N,N-diethyl-N′-methylethylenediamine, N,N,N′-triethylethylenediamine,3-dimethylaminopropylamine, 3-diethylaminopropylamine,3-dibutylaminopropylamine,N,N,N′-trimethyl-1,3-propanediamine,N,N,2,2-tetramethyl-1,3-propanediamine,2-amino-5-diethylaminopentane, N,N,N′,N′-tetraethyldiethylenetriamine,3,3′-diamino-N-methyldipropylamine,3,3′-iminobis(N,N-dimethylpropylamine), or combinations thereof. In suchembodiments, the resulting additive include a quaternary ammonium amidesalt, that is a detergent containing an amine and a quaternary ammoniumsalt.

In some embodiments the additives of the present invention are derivedfrom N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane,N,N-dimethylethylenediamine, N,N-diethylethylenediamine,N,N-dibutylethylenediamine, or combinations thereof.

The nitrogen or oxygen containing compounds may further includeaminoalkyl substituted heterocyclic compounds such as1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine,1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine,3,3-aminobis(N,N-dimethylpropylamine).

Another type of nitrogen or oxygen containing compounds capable ofcondensing with the acylating agent and having a tertiary amino groupinclude alkanolamines including but not limited to triethanolamine,N,N-dimethylaminopropanol, N,N-diethylaminopropanol,N,N-diethylaminobutanol, Triisopropanolamine,1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol,N-ethyldiethanolamine, N-methyldiethanol amine, N-butyldiethanolamine,N,N-diethylaminoethanol, N,N-dimethyl aminoethanol,2-dimethylamino-2-methyl-1-propanol. In embodiments where alkanolaminesand/or similar materials are used, the resulting additive includes aquaternary ammonium ester salt, that is a detergent containing an estergroup and a quaternary ammonium salt.

In one embodiment the nitrogen or oxygen containing compound isTriisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine,N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, or combinations thereof.

b. The Quaternizing Agent

The quaternized amide and/or ester detergents of the present inventionare formed when the non-quaternized detergents described above arereacted with a quaternizing agent. Suitable quaternizing agents includeselected dialkyl sulfates, benzyl halides, hydrocarbyl substitutedcarbonates; hydrocarbyl epoxides in combination with an acid or mixturesthereof.

In one embodiment, the quaternizing agent can include alkyl halides,such as chlorides, iodides or bromides; alkyl sulphonates; dialkylsulphates, such as, dimethyl sulphate; sultones; alkyl phosphates; suchas, C1-12 trialkylphosphates; di C1-12 alkylphosphates; borates; C1-12alkyl borates; alkyl nitrites; alkyl nitrates; dialkyl carbonates; alkylalkanoates; O,O-di-C1-12 alkyldithiophosphates; or mixtures thereof.

In one embodiment, the quaternizing agent may be derived from dialkylsulphates such as dimethyl sulphate, N-oxides, sultones such as propaneand butane sultone; alkyl, acyl or araalkyl halides such as methyl andethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl(or alkyl) substituted carbonates. If the alkyl halide is benzylchloride, the aromatic ring is optionally further substituted with alkylor alkenyl groups.

The hydrocarbyl (or alkyl) groups of the hydrocarbyl substitutedcarbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atomsper group. In one embodiment, the hydrocarbyl substituted carbonatescontain two hydrocarbyl groups that may be the same or different.Examples of suitable hydrocarbyl substituted carbonates include dimethylor diethyl carbonate.

In another embodiment, the quaternizing agent can be a hydrocarbylepoxide, as represented by the following formula, in combination with anacid:

wherein R¹, R², R³ and R⁴ can be independently H or a hydrocarbyl groupcontain from 1 to 50 carbon atoms. Examples of hydrocarbyl epoxidesinclude: ethylene oxide, propylene oxide, butylene oxide, styrene oxideand combinations thereof. In one embodiment the quaternizing agent doesnot contain any styrene oxide.

In some embodiments the acid used with the hydrocarbyl epoxide may be aseparate component, such as acetic acid. In other embodiments, forexample when the hydrocarbyl acylating agent is a dicarboxylic acylatingagent, no separate acid component is needed. In such embodiments, thedetergent may be prepared by combining reactants which are essentiallyfree to free of an acid component, such as acetic acid, and rely on theacid group of the hydrocarbyl acylating agent instead. In otherembodiments, a small amount of an acid component may be present, but at<0.2 or even <0.1 moles of acid per mole of hydrocarbyl acylating agent.

In certain embodiments the molar ratio of detergent having an aminefunctionality to quaternizing agent is 1:0.1 to 2, or 1:1 to 1.5, or 1:1to 1.3.

The Quaternized Amide and/or Ester Detergent Containing Compositions

The quaternized amide and/or ester detergents of the present inventionmay be used as an additive in various types of compositions, includingfuel compositions and additive concentrate compositions.

a. Fuel Compositions

The quaternized detergents of the present invention may be used as anadditive in fuel compositions. The fuel compositions of the presentinvention comprise the fuel additive described above and a liquid fuel,and is useful in fueling an internal combustion engine or an open flameburner. These compositions may also contain one or more additionaladditives. These optional additives are described below. In someembodiments, the fuels suitable for use in the present invention includeany commercially available fuel, and in some embodiments anycommercially available diesel fuel and/or biofuel.

The description that follows of the types of fuels suitable for use inthe present invention refer to the fuel that may be present in theadditive containing compositions of the present invention as well as thefuel and/or fuel additive concentrate compositions to which the additivecontaining compositions may be added.

Fuels suitable for use in the present invention are not overly limited.Generally, suitable fuels are normally liquid at ambient conditionse.g., room temperature (20 to 30° C.) or are normally liquid atoperating conditions. The fuel can be a hydrocarbon fuel,non-hydrocarbon fuel, or mixture thereof.

The hydrocarbon fuel can be a petroleum distillate, including a gasolineas defined by ASTM specification D4814, or a diesel fuel, as defined byASTM specification D975. In one embodiment the liquid fuel is agasoline, and in another embodiment the liquid fuel is a non-leadedgasoline. In another embodiment the liquid fuel is a diesel fuel. Thehydrocarbon fuel can be a hydrocarbon prepared by a gas to liquidprocess to include for example hydrocarbons prepared by a process suchas the Fischer-Tropsch process. In some embodiments, the fuel used inthe present invention is a diesel fuel, a biodiesel fuel, orcombinations thereof.

Suitable fuels also include heavier fuel oils, such as number 5 andnumber 6 fuel oils, which are also referred to as residual fuel oils,heavy fuel oils, and/or furnace fuel oils. Such fuels may be used aloneor mixed with other, typically lighter, fuels to form mixtures withlower viscosities. Bunker fuels are also included, which are generallyused in marine engines. These types of fuels have high viscosities andmay be solids at ambient conditions, but are liquid when heated andsupplied to the engine or burner it is fueling.

The non-hydrocarbon fuel can be an oxygen containing composition, oftenreferred to as an oxygenate, which includes alcohols, ethers, ketones,esters of a carboxylic acids, nitroalkanes, or mixtures thereof.Non-hydrocarbon fuels can include methanol, ethanol, methyl t-butylether, methyl ethyl ketone, transesterified oils and/or fats from plantsand animals such as rapeseed methyl ester and soybean methyl ester, andnitromethane.

Mixtures of hydrocarbon and non-hydrocarbon fuels can include, forexample, gasoline and methanol and/or ethanol, diesel fuel and ethanol,and diesel fuel and a transesterified plant oil such as rapeseed methylester and other bio-derived fuels. In one embodiment the liquid fuel isan emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or amixture thereof.

In several embodiments of this invention the liquid fuel can have asulphur content on a weight basis that is 50,000 ppm or less, 5000 ppmor less, 1000 ppm or less, 350 ppm or less, 100 ppm or less, 50 ppm orless, or 15 ppm or less.

The liquid fuel of the invention is present in a fuel composition in amajor amount that is generally greater than 95% by weight, and in otherembodiments is present at greater than 97% by weight, greater than 99.5%by weight, greater than 99.9% by weight, or greater than 99.99% byweight.

b. Additive Concentrate Compositions

Additive concentrates are compositions that contain one or moreadditives and which may also contain some amount of fuel, oil, or adiluent of some type. These concentrates can then be added to othercompositions as a convenient way to handle and deliver the additives,resulting in the final compositions such as the fuel compositionsdescribed above.

The additive concentrate compositions of the present invention containone or more of the quaternized detergents described above and anoptional diluent, which may be any of the fuels described above, asolvent, a diluent oil, or similar material. These compositions may alsocontain one or more of the additional additives described below.

c. Optional Additional Additives

The fuel and additive compositions of the present invention include thequaternized detergents described above and may also include one or moreadditional additives. Such additional performance additives can be addedto a fuel composition depending on several factors to include the typeof internal combustion engine and the type of fuel being used in thatengine, the quality of the fuel, and the service conditions under whichthe engine is being operated.

The additional performance additives can include: an antioxidant such asa hindered phenol or derivative thereof and/or a diarylamine orderivative thereof; a corrosion inhibitor; and/or a detergent/dispersantadditive, other than the fuel additive of the present invention, such asa polyetheramine or nitrogen containing detergent, including but notlimited to PIB amine detergents/dispersants, succinimidedetergents/dispersants, and other quaternary salt detergents/dispersantsincluding quaternary ammonium imide salts, that is a detergentcontaining an imide group and a quaternary ammonium salt.

The additional performance additives may also include: a cold flowimprover such as an esterified copolymer of maleic anhydride and styreneand/or a copolymer of ethylene and vinyl acetate; a foam inhibitorand/or antifoam agent such as a silicone fluid; a demulsifier such as apolyalkoxylated alcohol; a lubricity agent such as a fatty carboxylicacid; a metal deactivator such as an aromatic triazole or derivativethereof, including but not limited to benzotriazole; and/or a valve seatrecession additive such as an alkali metal sulfosuccinate salt.

Suitable antifoams also include organic silicones such as polydimethylsiloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylates andpolymethacrylates, trimethyl-trifluoro-propylmethyl siloxane and thelike.

The additional additives may also include a biocide; an antistaticagent, a deicer, a fluidizer such as a mineral oil and/orpoly(alpha-olefin) and/or polyether, and a combustion improver such asan octane or cetane improver.

The additional performance additives, which may be present in the fueladditive compositions and fuel compositions of the present invention,also include di-ester, di-amide, ester-amide, and ester-imide frictionmodifiers prepared by reacting a dicarboxylic acid (such as tartaricacid) and/or a tricarboxylic acid (such as citric acid), with an amineand/or alcohol, optionally in the presence of a known esterificationcatalyst. These friction modifiers, often derived from tartaric acid,citric acid, or derivatives thereof, may be derived from amines and/oralcohols that are branched, resulting in friction modifiers thatthemselves have significant amounts of branched hydrocarbyl groupspresent within it structure. Examples of suitable branched alcohols usedto prepare such friction modifiers include 2-ethylhexanol,isotridecanol, Guerbet alcohols, and mixtures thereof.

The additional performance additives may comprise a high TBN nitrogencontaining detergent/dispersant, such as a succinimide, that is thecondensation product of a hydrocarbyl-substituted succinic anhydridewith a poly(alkyleneamine). Succinimide detergents/dispersants are morefully described in U.S. Pat. Nos. 4,234,435 and 3,172,892.

Another class of nitrogen-containing detergent/dispersant is the Mannichbases. These are materials which are formed by the condensation of ahigher molecular weight, alkyl substituted phenol, an alkylenepolyamine, and an aldehyde such as formaldehyde. Such materials aredescribed in more detail in U.S. Pat. No. 3,634,515. Othernitrogen-containing detergents/dispersants include polymeric dispersantadditives, which are generally hydrocarbon-based polymers which containnitrogen-containing polar functionality to impart dispersancycharacteristics to the polymer.

An amine is typically employed in preparing the high TBNnitrogen-containing dispersant. One or more poly(alkyleneamine)s may beused, and these may comprise one or more poly(ethyleneamine)s having 3to 5 ethylene units and 4 to 6 nitrogen units. Such materials includetriethylenetetramine (TETA), tetraethylenepentamine (TEPA), andpentaethylenehexamine (PEHA). Such materials are typically commerciallyavailable as mixtures of various isomers containing a range number ofethylene units and nitrogen atoms, as well as a variety of isomericstructures, including various cyclic structures. The poly(alkyleneamine)may likewise comprise relatively higher molecular weight amines known inthe industry as ethylene amine still bottoms.

The additional performance additives may include quaternary ammoniumimide salts. In some embodiments the compositions of the presentinvention are substantially free to free of quaternary ammonium imidesalts. Quaternary ammonium imide salts are similar to the quaternaryammonium amide and/or ester salts of the present invention, except thatthe non-quaternized detergent/dispersant used in the preparation of theimide salts contains an imide group, instead of the amide and/or estergroup specified by the present invention.

The additional performance additives can each be added directly to theadditive and/or the fuel compositions of the present invention, but theyare generally mixed with the fuel additive to form an additivecomposition, or concentrate, which is then mixed with fuel to result ina fuel composition. The fuel compositions are described in more detailabove.

The Process of Preparing the Quaternized Amide and/or Ester Detergent

The present invention provides a process of preparing quaternized amideand/or ester detergent where the process includes: reacting (a) anon-quaternized amide and/or ester detergent having a tertiary aminefunctionality with (b) a quaternizing agent; thereby obtaining thequaternized detergent.

The processes of the present in invention may also be described as aprocess for preparing a quaternized amide and/or ester detergentcomprising the steps of: (1) mixing (a) a non-quaternized amide and/orester detergent having an amine functionality, (b) a quaternizing agentand (c) a protic solvent, which in some embodiments is free of methanol;(2) heating the mixture to a temperature between 50° C. to 130° C.; and(3) holding for the reaction to complete; thereby obtaining thequaternized amide and/or ester detergent. In one embodiment the reactionis carried out at a temperature of less than 80° C., or less then 70° C.In other embodiments the reaction mixture is heated to a temperature ofabout 50° C. to 120° C., 80° C., or 70° C. In still other embodimentswhere the hydrocarbyl acylating agent is derived from a monocarboxylicacid, the reaction temperature may be 70° C. to 130° C. In otherembodiments where the hydrocarbyl acylating agent is derived from adicarboxylic acid, the reaction temperature may be 50° C. to 80° C. or50° C. to 70° C.

In some embodiments the processes of the present invention are free ofthe addition of any acid reactant, such as acetic acid. The salt productis obtained in these embodiments despite the absence of the separateacid reactant.

As described above, in some embodiments the non-quaternized amide and/orester detergent is the condensation product of hydrocarbyl-substitutedacylating agent and a compound having an oxygen or nitrogen atom capableof condensing with said acylating agent and further having at least onetertiary amino group. Suitable quaternizing agents and compounds havingan oxygen or nitrogen atom are also described above.

a. The Protic Solvent

The additives of the present invention may be derived in the presence ofa protic solvent. In some embodiments the process used to prepare theseadditives is substantially free to free of methanol. Substantially freeof methanol can mean less than 0.5, 0.1 or 0.05 percent by weightmethanol in the reaction mixture, and may also mean completely free ofmethanol.

Suitable protic solvents include solvents that have dielectric constantsof greater than 9. In one embodiment the protic solvent includescompounds that contain 1 or more hydroxyl (—OH) functional groups, andmay include water.

In one embodiment, the solvents are glycols and glycol ethers. Glycolscontaining from 2 to 12 carbon atoms, or from 4 to 10, or 6 to 8 carbonatoms, and oligomers thereof (e.g., dimers, trimers and tetramers) aregenerally suitable for use. Illustrative glycols include ethyleneglycol, propylene glycol, diethylene glycol, dipropylene glycol,1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, triethyleneglycol, polyethylene glycol and the like and oligomers and polymericderivative and mixtures thereof. Illustrative glycol ethers include theC₁-C₆ alkyl ethers of propylene glycol, ethylene glycol and oligomersthereof such as di-, tri- and tetra glycol ethers of methyl, ethyl,propyl, butyl or hexyl. Suitable glycol ethers include ethers ofdipropylene glycol, tripropylene glycol diethylene glycol, triethyleneglycol; ethyl diglycol ether, butyl diglycol ether, methoxytriglycol,ethoxytriglycol, butoxytriglycol, methoxytetraglycol, butoxytetraglycol.

Suitable solvents for use in the invention also include certainalcohols. In one embodiment, these alcohols contain at least 2 carbonatoms, and in other embodiments at least 4, at least 6 or at least 8carbon atoms. In another embodiment, the solvent of the presentinvention contains 2 to 20 carbon atoms, 4 to 16 carbon atoms, 6 to 12carbon atoms, 8 to 10 carbon atoms, or just 8 carbon atoms. Thesealcohols normally have a 2-(C₁₋₄ alkyl) substituent, namely, methyl,ethyl, or any isomer of propyl or butyl. Examples of suitable alcoholsinclude 2-methylheptanol, 2-methyldecanol, 2-ethylpentanol,2-ethylhexanol, 2-ethylnonanol, 2-propylheptanol, 2-butylheptanol,2-butyloctanol, isooctanol, dodecanol, cyclohexanol, methanol, ethanol,propan-1-ol, 2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-1-ol,butan-2-ol, pentanol and its isomers, and mixtures thereof. In oneembodiment the solvent of the present invention is 2-ethylhexanol,2-ethyl nonanol, 2-propylheptanol, or combinations thereof. In oneembodiment the solvent of the present invention includes 2-ethylhexanol.

The solvent can be any of the commercially available alcohols ormixtures of such alcohols and also includes such alcohols and mixturesof alcohols mixed with water. In some embodiments the amount of waterpresent may be above 1 percent by weight of the solvent mixture. Inother embodiments the solvent mixture may contain traces of water, withthe water content being less than 1 or 0.5 percent by weight.

The alcohols can be aliphatic, cycloaliphatic, aromatic, orheterocyclic, including aliphatic-substituted cycloaliphatic alcohols,aliphatic-substituted aromatic alcohols, aliphatic-substitutedheterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substitutedheterocyclic alcohols, heterocyclic-substituted aliphatic alcohols,heterocyclic-substituted cycloaliphatic alcohols, andheterocyclic-substituted aromatic alcohols.

While not wishing to be bound by theory, it is believed that a polarprotic solvent is required in order to facilitate the dissociation ofthe acid into ions and protons. The dissociation is required toprotonate the ion formed when the detergent having an aminefunctionality initially reacts with the quaternizing agent. In the casewhere the quaternizing agent is an alkyl epoxide the resulting ion wouldbe an unstable alkoxide ion. The dissociation also provides a counterion from the acid group of the additive that acts to stabilize thequaternary ammonium ion formed in the reaction, resulting in a morestable product.

The solvent may be present such that the weight ratio of the amount ofdetergent having an amine functionality to the amount of polar solventis in one set of embodiments from 20:1 to 1:20; or from 10:1 to 1:10. Inadditional embodiments, the detergent to solvent weight ratio can befrom 1:10 to 1:15; from 15:1 to 10:1; or from 5:1 to 1:1.

INDUSTRIAL APPLICATION

In one embodiment, the process of the present invention produces aquaternized amide and/or ester detergent. The quaternized detergent canbe used as an additive for use in a fuel for use in an internalcombustion engine and/or an open flame burner.

The internal combustion engine includes spark ignition and compressionignition engines; 2-stroke or 4-stroke cycles; liquid fuel supplied viadirect injection, indirect injection, port injection and carburetor;common rail and unit injector systems; light (e.g. passenger car) andheavy duty (e.g. commercial truck) engines; and engines fuelled withhydrocarbon and non-hydrocarbon fuels and mixtures thereof. The enginesmay be part of integrated emissions systems incorporating such elementsas; EGR systems; aftertreatment including three-way catalyst, oxidationcatalyst, NOx absorbers and catalysts, catalyzed and non-catalyzedparticulate traps optionally employing fuel-borne catalyst; variablevalve timing; and injection timing and rate shaping.

The open flame burner burning may be any open-flame burning apparatusequipped to burn a liquid fuel. These include domestic, commercial andindustrial burners. The industrial burners include those requiringpreheating for proper handling and atomization of the fuel. Alsoincluded are oil fired combustion units, oil fired power plants, firedheaters and boilers, and boilers for use in ships and marineapplications including deep draft vessels. Included are boilers forpower plants, utility plants, and large stationary and marine engines.The open-flame fuel burning apparatus may be an incinerator such asrotary kiln incinerator, liquid injection kiln, fluidized bed kiln,cement kiln, and the like. Also included are steel and aluminum forgingfurnaces. The open-flame burning apparatus may be equipped with a fluegas recirculation system

The additives described above, in addition to being used as detergentsin fuel compositions, may also be used as a dispersant-type additive inlubricating oil compositions. Such lubricating compositions may comprisea minor amount of the quaternary ammonium salts described herein and amajor amount of an oil of lubricating viscosity. The specific levels atwhich the additive may be present are the same as those described abovefor the fuel compositions. The lubricating compositions may also containany of the optional additional additives described above.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form aring); substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

EXAMPLES

The invention will be further illustrated by the following examples.While the Examples are provided to illustrate the invention, they arenot intended to limit it.

Preparatory Material A

Polyisobutylene succinic anhydride (500 g), which itself is prepared byreacting 1000 number average molecular weight high vinylidenepolyisobutylene and maleic anhydride, is heated to 70° C. and charged toa jacketed reaction vessel fitted with stirrer, condenser, feed pumpattached to subline addition pipe, nitrogen line andthermocouple/temperature controller system. Heptane (76.9 grams) isadded to the reaction vessel and then dimethylaminopropylamine (52.3 g)is added over time, holding the reaction temperature at 70° C. Once theaddition is complete, the reaction vessel is held at 70° C. for 1 hour.The resulting product, a non-quaternized succinamide detergent, iscooled and collected.

Preparatory Material B

Polyisobutylene succinic anhydride (100 pbw) which itself is prepared byreacting 1000 number average molecular weight high vinylidenepolyisobutylene and maleic anhydride is heated to 80° C. and is chargedto a jacketed reaction vessel fitted with stirrer, condenser, feed pumpattached to subline addition pipe, nitrogen line andthermocouple/temperature controller system. The reaction vessel isheated to 100° C. Dimethylaminopropylamine (10.9 pbw) is charged to thereaction, maintaining the batch temperature below 120° C., over an 8hour period. The reaction mixture is then heated to 150° C. andmaintained at temperature for 4 hours. The resulting product, anon-quaternized succinimide detergent, is cooled and collected.

Comparative Example 1

Preparatory Material B, a non-quaternized succinimide detergent, (100pbw) is charged to a deck-scale reaction vessel. Acetic acid (5.9 pbw)and 2-ethylhexanol (38.4 pbw) are added to the vessel and the mixture isstirred and heated to 75° C. Propylene oxide (8.7 pbw) is added thereaction vessel over 4 hours, holding the reaction temperature at 75° C.The batch is held at temperature for 4 hours. The product, which isprimarily a quaternized succinimide detergent, is cooled and collected.

Comparative Example 2

Preparatory Material B, a non-quaternized succinimide detergent, (100pbw), is charged to a lab-scale reaction vessel. Acetic acid (5.8 pbw)and 2-ethylhexanol (38.4 pbw) are added to the vessel and the mixture isstirred and heated to 75° C. Propylene oxide (8.5 pbw) is added thereaction vessel over 4 hours, holding the reaction temperature at 75° C.The batch is held at temperature for 4 hours. The product, which isprimarily a quaternized succinimide detergent, is cooled and collected.

Example 3

Preparatory Material A, a non-quaternized succinamide detergent (470 g),is charged to a 2-liter round bottom flange flask with water condenserattached. 2-ethylhexanol (180.6 g) is added to the flask and the mixtureis stirred with an overhead stirrer and heated to 55° C. under anitrogen blanket. Propylene oxide (40.2 g) is then added to the reactionvessel via syringe pump over 4 hours, holding the reaction temperatureat 55° C. The batch is held at temperature for 16 hours. The product,which is primarily a quaternized succinamide detergent, is cooled andcollected.

The materials are tested to determine the extent of the reaction and todiscern between the amide and imide versions of the quaternary ammoniumsalt detergents produced. Electrospray Ionization (ESI) spectroscopy isused to analyze the samples, and using an internally developed protocol,the relative amounts of the imide containing structure, the amidecontaining structure and the tertiary amine (non-quaternized) structureare calculated. The results of this testing are presented in Table 1.

TABLE 1 ESI Mass Spec Results Percent Percent Percent Ex No Imide QuatAmide Quat Tertiary Amine Comp Ex 1 49 27 24 Comp Ex 2 69 12 19 Ex 3 885 7

The results show that Example 3 contains a major amount of a quaternizedsuccinamide detergent. The other examples all contain larger amounts ofthe quaternized succinimide detergent. Example 3 also shows the bestoverall conversion, at it has the smallest amount of tertiary amineremaining in the sample. The tertiary amine values representnon-quaternized detergent still present in the sample that was notquaternized in the reaction.

The examples are blended into DF-79 reference fuel, obtained fromHalternann Specialty Products, and are tested in a screen test using theCoordinating European Council's (CEC) F-98-08 DW10 testing protocol,which utilizes a Peugeot DW-10 engine. This is a light duty directinjection, common rail engine test that measures engine power loss,which relates to fuel detergent additive efficiency, where lower powerloss values indicate better detergent performance. The test engine isrepresentative of new engines coming into the market and the test methodis known in the field. The results of the engine testing are presentedin Table 2.

TABLE 2 DW10 Results Fuel Treat Rate of Additive Fuel Additive PercentFuel Sample Ex No (PPM) Power Loss A - Baseline None 0 3.9% B Comp Ex 173 2.8% C Ex 3 73 2.5%

The results show that when using fuel compositions containing theadditives of the present invention, Sample C, which contains thequaternized succinamide detergent of Example 3, gives slightly better,but comparable results to the Sample B, which contains the quaternizedsuccinimide detergent of Comparative Example 1.

The three additives prepared in the examples above are also tested in anoil compatibility test, which measures the compatibility of a fueladditive with engine oil additives. The test is considered a no harmtest in that it determines whether the fuel additive is compatible withengine oil additives it is likely to come into contact with during theoperation of an engine. The test procedure involves mixing the neat fueladditive with a neat engine oil additive package and then holding themixture at 90 degrees C. for 3 days. The mixture is then filtered. Testresults from the stability test include a pass/fail on whether themixture remains liquid or gels. Gelation is determined by a visualinspection of the sample. Test results also include a pass/fail onwhether the sample, if it remains liquid, can be within 3 minutes. Theresults of this testing is presented in Table 3.

TABLE 3 Oil Compatibility Testing Ex No Gel Check Filter Time Comp Ex 1PASS FAIL Comp Ex 2 PASS FAIL Ex 3 PASS PASS

The results show that the quaternized succinamide detergents additive ofthe present invention is more compatible with engine oil additives thanthe quaternized succinimide detergent additives of the comparativeexamples.

Two of the additives prepared in the examples above are also tested in athermal stability test. Samples of additives are stored at 100 degreesC. for 18 hours and then retested by FTIR, in order to evaluate theamount of thermal degradation of the additives that occurs. The resultsare presented in Table 4.

TABLE 4 Thermal Stability Testing FTIR FTIR Salt:HydrocarbonSalt:Hydrocarbon Ratio¹ Before Ratio¹ After Percent Difference Ex NoTesting Testing in Ratio Comp Ex 2 0.60 0.15 −75% Ex 3 0.58 0.41 −17%¹The salt has a FTIR spectra peak at 1560 cm⁻¹, and the hydrocarbon hasa FTIR peak at 1460 cm⁻¹. The values in the table above are the ratio ofthese peaks

Comparative Example 2 shows a 75% decrease of the salt hydrogen ratiorepresenting a significant reduction in the amount of quaternaryammonium salt present in the sample. This indicated that the additive ofComparative Example 2 is thermally degrading in significant amounts.

Example 3 shows a 17% decrease of the salt hydrogen ratio, which alsorepresents a reduction in the amount of quaternary ammonium saltpresent, but it is a significantly smaller reduction compared to thatfor Comparative Example 2. The results show that the quaternizedsuccinamide detergent additives of the present invention are morethermally stable than the quaternized succinimide detergent additives ofthe comparative examples.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Except where otherwise indicated, all numerical quantities inthe description specifying amounts or ratios of materials are on aweight basis. Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of” permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

We claim:
 1. A composition comprising a quaternary ammonium saltdetergent containing an amide group, where the quaternized detergentcomprises the reaction product of: (a) a non-quaternized detergentcontaining an amide group, where the detergent has a tertiary aminefunctionality; and (b) a quaternizing agent.
 2. The composition of claim1 wherein a protic solvent is present during the reaction of (a) and (b)and wherein the reaction of (a) and (b) is essentially free of anyadditional acid component other than any acid group present in thestructure of the detergent.
 3. The composition of claim 2 wherein theprotic solvent comprises a linear or branched alcohol containing 1 to 10carbon atoms.
 4. The composition of claim 1, wherein (a), thenon-quaternized detergent, comprises the condensation product of ahydrocarbyl-substituted acylating agent and a compound having an oxygenor nitrogen atom capable of condensing with said acylating agent andfurther having at least one tertiary amino group.
 5. The composition ofclaim 4, wherein the hydrocarbyl-substituted acylating agent comprisespolyisobutylene succinic anhydride.
 6. The composition of claim 4,wherein the compound having an oxygen nitrogen atom capable ofcondensing with said acylating agent comprises 1-aminopiperidine,1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-pipecoline,1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolidinyl)piperidine,1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine,N,N-diethylethylenediamine, N,N-dimethylethylenediamine,N,N-dibutylethylenediamine, N,N-dimethyl-1,3-diaminopropane,N,N-diethyl-1,3-diaminopropane, N,N-dibutyl-1,3-diaminopropane,N,N,N′-trimethylethylenediamine, N,N-dimethyl-N′-ethylethylenediamine,N,N-diethyl-N′-methylethylenediamine, N,N,N′-triethylethylenediamine,N,N,N′-trimethyl-1,3-propanediamine,N,N,2,2-tetramethyl-1,3-propanediamine, 2-amino-5-diethylaminopentane,N,N,N′,N′-tetraethyldiethylenetriamine,3,3′-diamino-N-methyldipropylamine,3,3′-iminobis(N,N-dimethylpropylamine), triethanolamine, or combinationsthereof.
 7. The composition of claim 4, wherein the compound having anoxygen nitrogen atom capable of condensing with said acylating agentcomprises N,N-diethylethylenediamine, N,N-dimethylethylenediamine,N,N-dibutylethylenediamine, N,N-dimethyl-1,3-diaminopropane,N,N-diethyl-1,3-diaminopropane, or combinations thereof.
 8. Thecomposition of claim 1, wherein (b), the quaternizing agent, comprisesethylene oxide, propylene oxide, butylene oxide, styrene oxide, orcombinations thereof.
 9. A fuel composition comprising the compositionof claim 1 and further comprising a fuel; and optionally furthercomprising one or more fuel additives other than the quaternary ammoniumsalt detergent.
 10. A method of operating an internal combustion engineor open flame burner comprising supplying to the engine or burner thefuel composition of claim
 9. 11. A process of making a quaternaryammonium salt detergent comprising: I. reacting (a) a non-quaternizeddetergent containing an amide group, where the detergent has a tertiaryamine functionality with (b) a quaternizing agent; thereby obtaining thequaternized detergent; wherein a protic solvent is present during thereaction of (a) and (b) and wherein the reaction of (a) and (b) is freeof any additional acid component other than any acid group present inthe structure of the detergent.
 12. The process of claim 11 wherein (a),the non-quaternized detergent, comprises the condensation product of ahydrocarbyl-substituted acylating agent and a compound having an oxygenor nitrogen atom capable of condensing with said acylating agent andfurther having at least one tertiary amino group.
 13. The process ofclaim 11 wherein (b), the quaternizing agent, comprises ethylene oxide,propylene oxide, butylene oxide, styrene oxide, or combinations thereof.14. The process of claim 11, wherein the process further comprises: II.heating the mixture of (a) to a temperature between about 50° C. toabout 130° C.; III. holding for the reaction to complete; therebyobtaining the quaternized dispersant.